C10-alkanolalkoxylate mixtures and the use thereof

ABSTRACT

The alkoxylate mixtures comprise alkoxylates of the formula (I)
 
C 5 H 11 CH(C 3 H 7 )CH 2 O(A) n (B) m H   (I)
 
where
         A is ethyleneoxy,   B is C 3-10 -alkyleneoxy or mixtures thereof,
 
where groups A and B may be present in random distribution, alternately or in the form of two or more blocks in any order,
   n is a number from 0 to 30,   m is a number from 0 to 20   n+m is at least 1
 
where
   70 to 99% by weight of alkoxylates A1 in which C 5 H 11  has the meaning n-C 5 H 11 , and   1 to 30% by weight of alkoxylates A2 in which C 5 H 11  has the meaning C 2 H 5 CH(CH 3 )CH 2  and/or CH 3 CH(CH 3 )CH 2 CH 2 ,
 
are present in the mixture.

The present invention relates to the use of C₁₀-alkanol alkoxylatemixtures, to C₁₀-alkanol alkoxylate mixtures of this type and toprocesses for their preparation.

Alkoxylates of aliphatic alcohols are used widely as surfactants,emulsifiers or foam-suppressing agents. The wetting and emulsifierproperties here depend heavily on the type of alcohol and on the typeand amount of the alkoxide adducts.

WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol indetergent compositions for degreasing hard surfaces. The alkoxylateshave 2 to 16 alkylene oxide groups. The majority of the alkylene oxidegroups is preferably in the form of ethylene oxide. According to theexamples, exclusively ethoxylated alcohols are used. It is alsodescribed that the alcohols can firstly be reacted with ethylene oxideand then with propylene oxide. However, no examples or properties aregiven for such alkoxylates. It is stated that the described alkoxylatesexhibit good detergency and wetting action, combined with low foaming.Additionally, it is stated that the alkoxylates have a desiredthickening effect in formulations.

WO 94/11330 relates to alkoxylates of 2-propylheptanol and to the usethereof. The alkoxylates contain 2-propylheptanol reacted firstly with 1to 6 mol of propylene oxide and then with 1 to 10 mol of ethylene oxide.According to the examples, a 2-propylheptanol reacted firstly with 4 molof propylene oxide and then with 6 mol of ethylene oxide is used. It isstated that the alkylene oxide adducts exhibit an improved ratio offoaming behavior to detergency. In addition, it is stated that thealkoxylates exhibit a good wetting behavior. They are used in detergentcompositions for cleaning textile materials.

U.S. Pat. No. 2,508,036 relates to the use of 2-n-propylheptanolethoxylates which contain 5 to 15 mol of ethylene oxide as wettingagents in aqueous solutions. It is described that the products can beused as surfactants in detergents. Processes for the alkoxylation of2-propylheptanol are known in principle from the prior art. WO 01/04183describes, for example, a process for the ethoxylation ofhydroxyfunctional starter compounds which is carried out in the presenceof a double-metal cyanide compound as catalyst.

It is an object of the present invention to provide alkanol alkoxylateswhich are suitable as emulsifier, foam regulator and as wetting agentfor hard surfaces. The alkoxylates should exhibit, in particular, goodemulsifying behavior and a low contact angle on hard surfaces upon use.In addition, they should reduce the interfacial tension in liquidsystems. The alkoxylates should in general exhibit an advantageousproperty spectrum when used as emulsifier, foam regulator or as wettingagent. Furthermore, the amount of residual alcohol should be reduced inorder to avoid unpleasant odors.

We have found that this object is achieved according to the invention byalkoxylate mixtures comprising alkoxylates of the formula (I)C₅H₁₁CH(C₃H₇)CH₂O(A)_(n)(B)_(m)H  (I)where

-   A is ethyleneoxy,-   B is C₃₋₁₀-alkyleneoxy, preferably propyleneoxy, butyleneoxy,    pentyleneoxy or mixtures thereof,    where groups A and B may be present in random distribution,    alternately or in the form of two or more blocks in any order,-   n is a number from 0 to 30,-   m is a number from 0 to 20-   n+m is at least 1    where-   70 to 99% by weight of alkoxylates A1 in which C₅H₁₁ has the meaning    n-C₅H₁₁, and-   1 to 30% by weight of alkoxylates A2 in which C₅H₁₁ has the meaning    C₂H₅CH(CH₃)CH₂ and/or CH₃CH(CH₃)CH₂CH₂,    are present in the mixture.

We have found that the above alkoxylate mixtures exhibit excellentemulsifier properties and can be used as nonfoaming or low-foamingwetting agents for hard surfaces. The alkoxylates exhibit low contactangles in the case of the wetting of hard surfaces and permit theestablishment of low interfacial tensions in liquid systems.

The alkoxylate mixtures of the formula (I) can thus particularlyadvantageously be used in particular as emulsifier, foam regulator andas wetting agent for hard surfaces in surfactant formulations forcleaning hard surfaces, in humectants, cosmetic, pharmaceutical and cropprotection formulations, paints, coating compositions, adhesives,leather degreasing compositions, formulations for the textile industry,fiber processing, metalworking, food industry, water treatment, paperindustry, fermentation, mineral processing and in emulsionpolymerizations. Further details on the individual fields of use aregiven below.

In the formula (I), n is preferably a number in the range from 0 to 30,in particular from 3 to 12. m is preferably a number in the range from 0to 8, in particular 1 to 8, particularly preferably 1 to 5. B ispreferably propyleneoxy and/or butyleneoxy.

In the alkoxylates according to the invention, propyleneoxy units canfirstly be joined to the alcohol radical, followed by ethyleneoxy units.If n and m have a value greater than 1, then the corresponding alkoxyradicals are preferably in block form. n and m refer here to a meanvalue, which arises as an average for the alkoxylates. n and m maytherefore also deviate from whole-number values. In the alkoxylation ofalkanols, a distribution of the degree of alkoxylation is generallyobtained, which can be adjusted to a certain extent through the use ofdifferent alkoxylation catalysts. In the alkoxylate mixtures accordingto the invention, it is also possible for ethyleneoxy units to firstlybe joined to the alcohol radical, followed by propyleneoxy units.Furthermore, random mixtures of ethylene oxide units and propylene oxideunits may be present. 3- or more-block alkoxylation and mixedalkoxylation are also possible. It is also possible that only ethyleneoxide units A or only units B, in particular propylene oxide units, arepresent. Through the choice of suitable amounts of groups A and B, thespectrum of properties of the alkoxylate mixtures according to theinvention can be adapted in each case to requirements in practice.Particular preference is given to carrying out the reaction firstly withpropylene oxide, butylene oxide, pentene oxide or mixtures thereof andsubsequently with ethylene oxide. It is, however, likewise possible forthe reaction to take place with ethylene oxide on its own.

Particularly preferably, in the formula (I), B is propyleneoxy. n isthen particularly preferably a number from 1 to 20, m is particularlypreferably a number from 1 to 8.

The alkoxylate mixtures according to the invention are obtained byalkoxylation of the parent alcohols C₅H₁₁CH(C₃H₇)CH₂OH. The startingalcohols can be mixed from the individual components, giving rise to theratio according to the invention. They can be prepared by aldolcondensation of valeraldehyde and subsequent hydrogenation. Thepreparation of valeraldehyde and the corresponding isomers takes placeby hydroformylation of butene, as described, for example, in U.S. Pat.No. 4,287,370; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia ofIndustrial Chemistry, 5th Edition, Volume A1, pages 323 and 328 f. Thesubsequent aldol condensation is described, for example, in U.S. Pat.No. 5,434,313 and Römpp, Chemie Lexikon, 9th Edition, keyword“Aldol-Addition” page 91. The hydrogenation of the aldol condensationproduct follows general hydrogenation conditions.

Furthermore, 2-propylheptanol can be prepared by condensation of1-pentanol (as a mixture of the corresponding 1-methylbutanols) in thepresence of KOH at elevated temperatures, see e.g. Marcel Guerbet, C.R.Acad Sci Paris 128, 511, 1002 (1899). Furthermore, reference is made toRömpp, Chemie Lexikon, 9th Edition, Georg Thieme Verlag Stuttgart, andthe citations given therein, and also to Tetrahedron, Vol. 23, pages1723 to 1733.

In the formula (I), the radical C₅H₁₁ can have the meaning n-C₅H₁₁,C₂H₅CH(CH₃)CH₂ or CH₃CH(CH₃)CH₂CH₂. The alkoxylates are mixtures where70 to 99% by weight, preferably 85 to 96% by weight, of alkoxylates A1are present in which C₅H₁₁ has the meaning n-C₅H₁₁, and

-   1 to 30% by weight, preferably 4 to 15% by weight, of alkoxylates A2    in which C₅H₁₁ has the meaning C₂H₅CH(CH₃)CH₂ and/or    CH₃CH(CH₃)CH₂CH₂.

The radical C₃H₇ preferably has the meaning n-C₃H₇.

The alkoxylation is preferably catalyzed by strong bases, which areexpediently added in the form of an alkali metal alkoxide, an alkalimetal hydroxide or alkaline earth metal hydroxide, usually in an amountof from 0.1 to 1% by weight, based on the amount of alkanol R²—OH (cf.G. Gee et al., J. Chem. Soc. (1961), p. 1345; B. Wojtech, Makromol.Chem. 66, (1966), p. 180).

An acidic catalysis of the addition reaction is also possible. Inaddition to Bronsted acids, Lewis acids are also suitable, such as, forexample, AlCl₃ or BF₃ dietherate, BF₃, BF₃×H₃PO₄, SbCl₄×2H₂O,hydrotalcite (cf. P. H. Plesch, The Chemistry of CationicPolymerization, Pergamon Press, New York (1963). Double-metal cyanide(DMC) compounds are also suitable as catalyst.

As DMC compounds it is possible in principle to use all suitablecompounds known to the person skilled in the art.

DMC compounds suitable as catalyst are described, for example, in WO99/16775 and DE 10117273. In particular, double-metal cyanide compoundsof the general formula I are suitable as catalyst for the alkoxylation:M¹ _(a)[M²(CN)_(b)(A)_(c)]_(d) .fM¹ _(g) X _(n) .h(H₂O).eL.kP  (I)in which

-   -   M¹ is at least one metal ion, chosen from the group consisting        of Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Mo⁴⁺,        Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺, Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺,        Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺,        Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺, Ru²⁺, Ru³⁺,    -   M² is at least one metal ion, chosen from the group consisting        of Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺, Cr²⁺, Cr³⁺,        Rh³⁺, Ru²⁺, Ir³⁺,    -   A and X, independently of one another, are an anion chosen from        the group consisting of halide, hydroxide, sulfate, carbonate,        cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate,        nitrate, nitrosyl, hydrogensulfate, phosphate,        dihydrogenphosphate, hydrogenphosphate or hydrogencarbonate,    -   L is a water-miscible ligand chosen from the group consisting of        alcohols, aldehydes, ketones, ethers, polyethers, esters,        polyesters, polycarbonate, ureas, amides, primary, secondary and        tertiary amines, ligands with pyridine nitrogen, nitriles,        sulfides, phosphides, phosphites, phosphines, phosphonates and        phosphates,    -   k is a fraction or integer greater than or equal to zero, and    -   P is an organic additive,    -   a, b, c, d, g and n are chosen such that the electron neutrality        of the compound (I) is ensured, where c may =0,    -   e is the number of ligand molecules, a fraction or integer        greater than 0, or 0,    -   f and h, independently of one another, are a fraction or integer        greater than 0 or 0.

Organic additives P to be mentioned are: polyethers, polyesters,polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycolglycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid),polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile,polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether,polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol,poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid),polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylicacid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acidand maleic anhydride copolymers, hydroxyethylcellulose, polyacetates,ionic surface- and interface-active compounds, bile acid or saltsthereof, esters or amides, carboxylic esters of polyhydric alcohols andglycosides.

These catalysts can be crystalline or amorphous. Where k is zero,crystalline double-metal cyanide compounds are preferred. Where k isgreater than zero, preference is given to crystalline, partiallycrystalline and also substantially amorphous catalysts.

There are various preferred embodiments of the modified catalysts. Apreferred embodiment covers catalysts of the formula (I) in which k isgreater than zero. The preferred catalyst then comprises at least onedouble-metal cyanide compound, at least one organic ligand and at leastone organic additive P.

In another preferred embodiment, k is zero, e is optionally also equalto zero and X is exclusively a carboxylate, preferably formate, acetateand propionate. Such catalysts are described in WO 99/16775. In thisembodiment, preference is given to crystalline double-metal cyanidecatalysts. Also preferred are double-metal cyanide catalysts, asdescribed in WO 00/74845, which are crystalline and plate-like.

The modified catalysts are prepared by combining a metal salt solutionwith a cyanometallate solution, which may optionally contain both anorganic ligand L and also an organic additive P. The organic ligand andoptionally the organic additive are then added. In a preferredembodiment of the catalyst preparation, an inactive double-metal cyanidephase is firstly prepared, and this is then converted into an activedouble-metal cyanide phase by recrystallization, as described inPCT/EP01/01893.

In another preferred embodiment of the catalysts, f, e and k do notequal zero. These are double-metal cyanide catalysts which contain awater-miscible organic ligand (generally in amounts of from 0.5 to 30%by weight) and an organic additive (generally in amounts of from 5 to80% by weight), as described in WO 98/06312. The catalysts can either beprepared with vigorous stirring (24 000 rpm using Turrax) or withstirring, as described in U.S. Pat. No. 5,158,922.

Catalysts which are particularly suitable for the alkoxylation aredouble-metal cyanide compounds which contain zinc, cobalt or iron or twoof these. For example, Berlin Blue is particularly suitable.

Preference is given to using crystalline DMC compounds. In a preferredembodiment, a crystalline DMC compound of the Zn—Co type which compriseszinc acetate as further metal salt component is used as catalyst. Suchcompounds crystallize in monoclinic structure and have a plate-likehabit. Such compounds are described, for example, in WO 00/74845 orPCT/EP01/01893.

DMC compounds suitable as catalyst can, in principle, be prepared by allmethods known to the person skilled in the art. For example, the DMCcompounds can be prepared by direct precipitation, “incipient wetness”method, by preparing a precursor phase and subsequent recrystallization.

The DMC compounds can be used as powder, paste or suspension, or beshaped to give a shaped body, be introduced into shaped bodies, foams orthe like, or be applied to shaped bodies, foams or the like.

The catalyst concentration used for the alkoxylation, based on the finalquantity structure, is typically less than 2 000 ppm (i.e. mg ofcatalyst per kg of product), preferably less than 1 000 ppm, inparticular less than 500 ppm, particularly preferably less than 100 ppm,for example less than 50 ppm or 35 ppm, in particular preferably lessthan 25 ppm.

The addition reaction is carried out at temperatures of from about 90 to240° C., preferably from 120 to 180° C., in a closed vessel. Thealkylene oxide or the mixture of different alkylene oxides is added tothe mixture of alkanol mixture according to the invention and alkaliunder the vapor pressure of the alkylene oxide mixture which prevails atthe chosen reaction temperature. If desired, the alkylene oxide can bediluted by up to about 30 to 60% with an inert gas. This ensuresadditional safety against explosion-like polyaddition of the alkyleneoxide.

If an alkylene oxide mixture is used, then polyether chains are formedin which the various alkylene oxide building blocks are distributed in avirtually random manner. Variations in the distribution of the buildingblocks along the polyether chain arise on the basis of differentreaction rates of the components and can also be achieved voluntarilythrough the continuous introduction of an alkylene oxide mixture ofprogram-controlled composition. If the different alkylene oxides arereacted one after the other, polyether chains are obtained which have ablock-like distribution of the alkylene oxide building blocks.

The length of the polyether chains varies within the reaction productstatistically about an average value which essentially corresponds tothe stoichiometric value which arises from the amount added.

Preferred alkoxylate mixtures of the formula (I) can be obtainedaccording to the invention by reacting alcohols of the formulaC₅H₁₁CH(C₃H₇)CH₂OH firstly with propylene oxide and then with ethyleneoxide under alkoxylation conditions or only with ethylene oxide.Suitable alkoxylation conditions are described above and in NikolausSchönfeldt, Grenzflächenaktive Äthylenoxid-Addukte [Interface-activeethylene oxide adducts], Wissenschaftliche Verlagsgesellschaft mbHStuttgart, 1984. The alkoxylation is generally carried out in thepresence of basic catalysts such as KOH without a diluent. However, thealkoxylation can also be carried out with the co-use of a solvent. Toprepare these alkoxylate mixtures according to the invention, thealcohols are firstly reacted with a suitable amount of propylene oxideand then with a suitable amount of ethylene oxide, or only with ethyleneoxide. In the process, a polymerization of the alkylene oxide is set inmotion in which a random distribution of homologues inevitably results,the average value of which is given in the present case by n and m.

As a result of the propoxylation preferably carried out first accordingto the invention and ethoxylation which is only carried outsubsequently, it is possible to reduce the content of residual alcoholin the alkoxylates since propylene oxide is added more uniformly to thealcohol component. In contrast thereto, ethylene oxide preferably reactswith ethoxylates, meaning that in the case of an initial use of ethyleneoxide for the reaction with the alkanols, both a broad homologuedistribution and also a high content of residual alcohol result. Theavoidance of relatively large amounts of residual alcohol present in theproduct is particularly advantageous for odor reasons. The alcoholmixtures used according to the invention generally have an intrinsicodor which can be largely suppressed by complete alkoxylation.Alkoxylates obtained by customary processes often have an intrinsic odorwhich is undesired for many applications.

Surprisingly, it has been found that this effect occurs even when theamounts of propylene oxide used are small, i.e. in accordance with theinvention less than 1.5 equivalents, based on the alcohol used, inparticular less than 1.2 equivalents, particularly preferably less than1 equivalent.

The alkoxylate mixtures according to the invention require only onepropylene oxide (PO) block of very short length bonded directly to thealcohol to reduce the residual alcohol content. This is thereforeparticularly very advantageous as the biodegradability of the productdecreases as the PO block is extended. Such alkoxylate mixtures thuspermit maximum degrees of freedom in the choice of the length of the POblock, the length downwards being limited by the increasing residualalcohol content, and upwards by the deterioration in thebiodegradability. This is then particularly advantageous when only ashort ethylene oxide block follows the PO block.

For the purposes of the present invention, it is therefore furtherpreferred that m is an integer or fraction where 0<m≦5, for example0<m≦2, preferably 0<m≦1.5, particularly preferably 0<m≦1.2, inparticular 0<m<1.

According to the invention, it is not necessary for a large residualcontent of alcohol to be present in the alkoxylate mixtures according tothe invention. According to one embodiment of the invention, thealkoxylate mixtures have a reduced alcohol content.

The alkoxylate mixtures according to the invention exhibit improvedwetting on hard surfaces.

The advantageous wetting behavior of the mixtures according to theinvention can, for example, be determined by measuring the contact angleon glass, polyethylene oxide or steel. The improved wetting behaviorleads to better performance in the case, in particular, of rapidcleaning processes. This is surprising since the chain lengthening ofthe starting alcohol usually diminishes the dynamic and wettingproperties. The alkoxylate mixtures according to the invention can thusbe used to increase the wetting rate of aqueous formulations. Thealkoxylate mixtures according to the invention can thus also be used assolubilizers which, in particular, do not have a negative effect on thewetting ability of wetting auxiliaries even in dilute systems, but havea positive effect. They can be used for increasing the solubility ofwetting auxiliaries in aqueous formulations which comprise nonionicsurfactants. In particular, they are used for increasing the wettingrate in aqueous wetting agents.

In addition, the alkoxylate mixtures according to the invention are usedfor reducing interfacial tension, for example in aqueous surfactantformulations. The reduced interfacial tension can be determined, forexample, by the pendant drop method. From this also arises a betteraction of the alkoxylate mixtures according to the invention asemulsifier or coemulsifier. The alkoxylate mixtures according to theinvention can also be used for reducing the interfacial tension in shorttimes of, customarily, less than one second or for accelerating theestablishment of the interfacial tension in aqueous surfactantformulations.

The present invention likewise provides cleaning, wetting, coating,adhesive, leather degreasing, humectant or textile-treatmentcompositions or cosmetic, pharmaceutical or crop protection formulationswhich comprise at least one alkoxylate mixture of the formula (I) asdefined above. The compositions preferably comprise 0.1 to 20% by weightof the alkoxylate mixtures. Preferred fields of use for the alkoxylatemixtures according to the invention are described in more detail below.

The alkoxylate mixtures according to the invention are preferably usedin the following areas:

-   -   Surfactant formulations for cleaning hard surfaces: suitable        surfactant formulations to which the alkoxylates according to        the invention can be added are described, for example, in        Formulating Detergents and Personal Care Products by Louis Ho        Tan Tai, AOCS Press, 2000.    -   They comprise, for example as further components, soaps, anionic        surfactants such as LAS or paraffin sulfonates or FAS or FAES,        acid, such as phosphoric acid, amidosulfonic acid, citric acid,        lactic acid, acetic acid, other organic and inorganic acids,        solvents, such as ethylene glycol, isopropanol, complexing        agents, such as EDTA, NTA, MGDA, phosphonates, polymers, such as        polyacrylates, maleic acid-acrylic acid copolymers, alkali        donors, such as hydroxides, silicates, carbonates, perfume oils,        oxidizing agents, such as perborates, peracids or        trichloroisocyanuric acid, Na or K dichloroisocyanurates,        enzymes; see also Milton J. Rosen, Manilal Dahanayake,        Industrial Utilization of Surfactants, AOCS Press, 2000 and        Nikolaus Schönfeldt, Grenzflächenaktive Ethylenoxidaddukte        [Interface-active ethylene oxide adducts]. These also in        principle cover formulations for the other said applications.        These may be household cleaners, such as all-purpose cleaners,        dishwashing detergents for manual and automatic dishwashing,        metal degreasing, industrial applications such as cleaners for        the food industry, bottle washing, etc. They may also be        printing roll and printing plate cleaning compositions in the        printing industry. Suitable further ingredients are known to the        person skilled in the art.    -   Humectants, in particular for the printing industry.    -   Cosmetic, pharmaceutical and crop protection formulations.        Suitable crop protection formulations are described, for        example, in EP-A-0 050 228. Further ingredients customary for        crop protection compositions may also be present.    -   Paints, coating compositions, inks, pigment preparations and        adhesives in the coating and polymer film industry.    -   Leather degreasing compositions.    -   Formulations for the textile industry, such as leveling agents        or formulations for yarn cleaning.    -   Fiber processing and auxiliaries for the paper and pulp        industry.    -   Metal processing, such as metal refining and electroplating        sector.    -   Food industry.    -   Water treatment and drinking water production.    -   Fermentation.    -   Mineral processing and dust control.    -   Building auxiliaries.    -   Emulsion polymerization and preparation of dispersions.    -   Coolants and lubricants.

Such formulations usually comprise ingredients such as surfactants,builders, fragrances and dyes, complexing agents, polymers and otheringredients. Typical formulations are described, for example, in WO01/32820. Further ingredients suitable for different applications aredescribed in EP-A-0 620 270, WO 95/27034, EP-A-0 681 865, EP-A-0 616026, EP-A-0 616 028, DE-A42 37 178 and U.S. Pat. No. 5,340,495 and inSchönfeldt, see above, by way of example.

In general, the alkoxylate mixtures according to the invention can beused in all fields where the action of interface-active substances isnecessary.

The structures according to the invention have low aquatoxicity and goodbiodegradability compared to known structures, meaning that they areadvantageously suitable for a large number of fields of application.

The present invention is described in more detail below by reference toexamples.

EXAMPLES Preparation Example 1 DMC Catalyst

16 000 g of aqueous hexacyanocobaltic acid (cobalt content: 9 g/l) wereintroduced into a stirred-tank reactor with a volume of 30 l, fittedwith propeller stirrer, submerged tube for metered addition, pH probeand scattered light probe, and heated to 50° C. with stirring. Then,with stirring at a stirrer speed of 0.4 W/l, 9 224 g of aqueous zincacetate dihydrate solution (zinc content: 2.6% by weight), which waslikewise heated to 50° C., were introduced over the course of 15minutes.

351 g of Pluronic® PE 6200 (BASF AG) were added to this precipitationsuspension, and the mixture was stirred for a further 10 minutes.

A further 3 690 g of aqueous zinc acetate dihydrate solution (zinccontent: 2.6% by weight) were then metered in with stirring at astirring energy of 1 W/l over the course of 5 minutes.

The suspension was after-stirred for two hours. During this time, the pHdropped from 4.02 to 3.27 and then remained constant. The precipitationsuspension obtained in this way was then filtered off and washed on thefilter with 6 times the cake volume of water.

The moist filter cake was dried and dispersed in Tridekanol® N using agap rotor mill. The resulting suspension had a multimetal cyanidecontent of 5% by weight.

Example 1 2-propylheptanol+5 EO, 25 ppm of DMC

474 g (3.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% 2-propyl-4-methyl-1-hexanol, <1%2-propyl-5-methyl-1-hexanol) and 0.567 g of 5% strength suspension ofdouble-metal cyanide in 2-propylheptanol isomer mixture (25 ppm based onthe product) as catalyst were dehydrated at a temperature of 80° C. andabout 1 mbar, then placed in a 2 l pressurized autoclave, flushed threetimes with nitrogen and then heated to 120° C. After the temperature hadbeen reached, 660 g (15 mol) of ethylene oxide were continuously meteredin over 1.05 hours at a pressure of from 0.1 to 3.7 bar (pressure ramp 6bar/90 min). Following the addition of all of the oxide, the mixture wasleft to react until the pressure was constant (20 minutes), then cooledto 80° C., flushed three times with nitrogen and emptied. The resultingproduct was degassed at 80° C. on a rotary evaporator under reducedpressure (<30 mbar) (reaction product not filtered).

Example 2 2-propylheptanol+3 EO, 25 ppm of DMC

The reaction was carried out analogously to example 1 with 474 g (3.0mol) of 2-propylheptanol isomer mixture, 0.44 g of double-metal cyanidesuspension and 397 g (9.0 mol) of ethylene oxide.

Example 3 2-propylheptanol+8 EO, 25 ppm of DMC

The reaction was carried out analogously to example 1 with 474 g (3.0mol) of 2-propylheptanol isomer mixture, 0.77 g of double-metal cyanidesuspension and 1 060 g (24.0 mol) of ethylene oxide.

Preparation Example 2 Synthesis of Ethoxylates of 2-propylheptanol byMeans of KOH Catalysis

2-Propylheptanol and KOH (finely powdered) were mixed and dehydrated at80° C. and 40 mbar for 1 hour. The reaction product was introduced intoan autoclave, the autoclave was rendered inert twice with nitrogen andthen heated to 120° C. Over the course of 15 minutes, ethylene oxide wasmetered in to a maximum pressure of 1 bar. The system was maintained for5 min at this pressure, then the pressure was increased to 3 bar byadding ethylene oxide over the course of 60 min, the system was held atthis pressure for 5 hours, and finally the pressure was increased to 6bar. During the last metered addition, ethylene oxide was added onlyuntil the desired amount of ethylene oxide was reached. The pressure wasthen maintained at 6 bar through the metered addition of nitrogen. Aftera reaction time of a further 10 hours, the system was left to cool to80° C., and the reaction product was discharged. Volatile componentswere removed on a rotary evaporator at 30 mbar and 80° C.

Example 4 2-propylheptanol+3 EO, KOH Catalyzed

The synthesis was carried out analogously to preparation example 2.474 gof 2-propylheptanol (3.0 mol), 397 g of ethylene oxide (9.0 mol) and 1.8g of KOH were used.

a) The starting alcohol used was pure 2-PH, prepared by distillation ofthe technical-grade mixture with a purity greater than 99%. The producthas the following properties:

-   Wetting on textile surfaces (EN 1772): 13 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): about 20 ml (40° C.; 2 g/l; 1.8 mmol of    Ca²⁺ ions, after 30 sec)-   Surface tension (DIN 53914): about 26.8 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 3.1 mol of EO

b) The starting alcohol used was 2-propylheptanol, technical-gradequality with about 90% of 2-Ph and about 10% of4-methyl-2-propylhexanol. The product has the following properties:

-   Wetting on textile surfaces (EN 1772): 12 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): about 20 ml (40° C.; 2 g/l; 1.8 mmol of    Ca²⁺ ions, after 30 sec)-   Surface tension (DIN 53914): about 27.2 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 2.8 mol of EO

Example 5 2-propylheptanol+5 EO, KOH Catalyzed

The synthesis was carried out analogously to preparation example 2.474 gof 2-propylheptanol (3.0 mol), 661 g of ethylene oxide (15.0 mol) and2.3 g of KOH were used.

a) The starting alcohol used was pure 2-PH, prepared by distillation ofthe technical-grade mixture with a purity greater than 99%. The producthas the following properties:

-   Wetting on textile surfaces (EN 1772): 10 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 25 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): about 27.1 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 5.2 mol of EO

b) The starting alcohol used was 2-propylheptanol, technical-gradequality with about 90% of 2-Ph and about 10% of4-methyl-2-propylhexanol. The product has the following properties:

-   Wetting on textile surfaces (EN 1772): 9 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 30 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): about 26.3 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 4.6 mol of EO

Example 6 2-propylheptanol+7 EO, KOH Catalyzed

The synthesis was carried out analogously to preparation example 2.474 gof 2-propylheptanol (3.0 mol), 925 g of ethylene oxide (21.0 mol) and2.8 g of KOH were used.

a) The starting alcohol used was pure 2-PH, prepared by distillation ofthe technical-grade mixture with a purity greater than 99%. The producthas the following properties:

-   Wetting on textile surfaces (EN 1772): 14 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 330 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): about 27.8 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 7.4 mol of EO

b) The starting alcohol used was 2-propylheptanol, technical-gradequality with about 90% of 2-Ph and about 10% of4-methyl-2-propylhexanol. The product has the following properties:

-   Wetting on textile surfaces (EN 1772): 13 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 350 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): about 27.1 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 7.1 mol of EO

Example 7 2-propylheptanol+10 EO, KOH Catalyzed

The synthesis was carried out analogously to preparation example 2.474 gof 2-propylheptanol (3.0 mol), 1 322 g of ethylene oxide (30.0 mol) and3.6 g of KOH were used.

a) The starting alcohol used was pure 2-PH, prepared by distillation ofthe technical-grade mixture with a purity greater than 99%. The producthas the following properties:

-   Wetting on textile surfaces (EN 1772): 47 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 380 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): 30.5 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 10.4 mol of EO

b) The starting alcohol used was 2-propylheptanol, technical-gradequality with about 90% of 2-Ph and about 10% of4-methyl-2-propylhexanol. The product has the following properties:

-   Wetting on textile surfaces (EN 1772): 40 sec (23° C., 1 g/l in 2 g    of soda/l)-   Foaming ability (EN 12728): 370 ml (40° C.; 2 g/l; 1.8 mmol of Ca²⁺    ions, after 30 sec)-   Surface tension (DIN 53914): about 30.7 mN/m (1 g/l; 23° C.)-   Degree of ethoxylation acc. to OH number: 10.2 mol of EO

The physicochemical properties and tests for wetting, foam etc. thusexhibit comparable performance irrespective of whether the preparationwas carried out using a technical grade or isomerically pure grade.

Example 8 Alkoxylation with EO with DMC Catalyst

8.1 2-Propylheptanol+3 EO

316 g (2.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% 2-propyl-4-methyl-1-hexanol, <1% of2-propyl-5-methyl-1-hexanol) and 35 ppm of double-metal cyanide catalyst(based on the product) were dehydrated at a temperature of 100° C. andabout 20 mbar for 2 hours in a pressurized autoclave. The mixture wasthen flushed three times with nitrogen and heated to 140° C. After thetemperature has been reached, a total of 264 g (6.0 mol) of ethyleneoxide were metered in with stirring. When the ethylene oxide meteredaddition was complete, the mixture was stirred for a further 1 h at 140°C., and the reactor was flushed three times with nitrogen, thenevacuated to degas to 20 mbar, then cooled to 80° C., and emptied. Thereaction product was not filtered.

-   Residual alcohol content (2-propyl-1-heptanol): 9.6%    8.2 2-Propylheptanol+4 EO

The procedure was as in example 8.1. However, 8.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 5.8%    8.3 2-Propylheptanol+5 EO

The procedure was as in example 8.1. However, 10.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 2.7%    8.4 2-Propylheptanol+6 EO

The procedure was as in example 8.1. However, 12.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 1.4%    8.5 2-Propylheptanol+7 EO

The procedure was as in example 8.1. However, 14.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.8%    8.6 2-Propylheptanol+8 EO

The procedure was as in example 8.1. However, 16.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.3%    8.7 2-Propylheptanol+10 EO

The procedure was as in example 8.1. However, 20.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.2%    8.8 2-Propylheptanol+14 EO

The procedure was as in example 8.1. However, 28.0 mol of ethylene oxideinstead of 6.0 mol were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.1%

Example 9 Alkoxylation with PO with DMC Catalyst

9.1 2-Propylheptanol+0.8 PO

316 g (2.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% of 2-propyl-4-methyl-1-hexanol, <1% of2-propyl-5-methyl-1-hexanol) and 35 ppm of double-metal cyanide catalyst(based on the product) were dehydrated at a temperature of 100° C. andabout 20 mbar for two hours in a pressurized autoclave. The system wasthen flushed three times with nitrogen and then heated to 140° C. Afterthe temperature had been reached, a total of 93 g (1.6 mol) of propyleneoxide were metered in at 140° C. with stirring. When the PO meteredaddition was complete, the mixture was stirred for a further 15 minutesat 140° C., and the reactor was flushed three times with nitrogen, thenevacuated to degas to 20 mbar, then cooled to 80° C., and emptied.

-   Residual alcohol content (2-propyl-1-heptanol): 28.6%    9.2 2-Propylheptanol+1.0 PO

The procedure was as in example 9.1. However, 2.0 mol of propylene oxideinstead of 1.6 mol were added, and the process was carried out at areaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 24.2%    9.3 2-Propylheptanol+1.20 PO

The procedure was as in example 9.1. However, 2.4 mol of propylene oxideinstead of 1.6 mol were added, and the process was carried out at areaction temperature of 160° C.

-   Residual alcohol content (2-propyl-1-heptanol): 20.0%    9.4 2-Propylheptanol+1.20 PO

The procedure was as in example 9.1. However, 2.4 mol of propylene oxideinstead of 1.6 mol were added, and the process was carried out at areaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 19.8%    9.5 2-Propylheptanol+1.23 PO

The procedure was as in example 9.1. However, 2.46 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 120° C.

-   Residual alcohol content (2-propyl-1-heptanol): 20.8%    9.6 2-Propylheptanol+1.28 PO

The procedure was as in example 9.1. However, 2.56 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 17.7%    9.7 2-Propylheptanol+1.30 PO

The procedure was as in example 9.1. However, 2.6 mol of propylene oxideinstead of 1.6 mol were added, and the process was carried out at areaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 17.6%    9.8 2-Propylheptanol+1.40 PO

The procedure was as in example 9.1. However, 2.8 mol of propylene oxideinstead of 1.6 mol were added, and the process was carried out at areaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 15.8%    9.9 2-Propylheptanol+1.44 PO

The procedure was as in example 9.1. However, 2.88 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 140° C.

-   Residual alcohol content (2-propyl-1-heptanol): 14.8%    9.10 2-Propylheptanol+1.51 PO

The procedure was as in example 9.1. However, 3.02 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 120° C.

-   Residual alcohol content (2-propyl-1-heptanol): 15.0%    9.11 2-Propylheptanol+1.63 PO

The procedure was as in example 9.1. However, 3.26 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 160° C.

-   Residual alcohol content (2-propyl-1-heptanol): 10.1%    9.12 2-Propylheptanol+1.71 PO

The procedure was as in example 9.1. However, 3.42 mol of propyleneoxide instead of 1.6 mol were added, and the process was carried out ata reaction temperature of 120° C.

-   Residual alcohol content (2-propyl-1-heptanol): 10.7%

Example 10 Alkoxylation with PO and EO with DMC Catalyst

10.1 2-Propylheptanol+0.8 PO+3 EO

316 g (2.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% of 2-propyl-4-methyl-1-hexanol, <1% of2-propyl-5-methyl-1-hexanol) and 35 ppm of double-metal cyanide catalyst(based on the product) were dehydrated at a temperature of 100° C. andabout 20 mbar for two hours in a pressurized autoclave. The system wasthen flushed three times with nitrogen and then heated to 140° C. Afterthe temperature had been reached, a total of 93 g (1.6 mol) of propyleneoxide were metered in at 140° C. with stirring. When the PO meteredaddition was complete, the mixture was stirred for a further 15 minutesat 140° C., and then the metered addition of a total of 264 g (6.0 mol)of ethylene oxide was started. When the ethylene oxide metered additionwas complete, the mixture was stirred for a further 1 h at 140° C., andthe reactor was flushed three times with nitrogen, then evacuated todegas to 20 mbar, then cooled to 80° C., and emptied. The reactionproduct was not filtered.

-   Residual alcohol content (2-propyl-1-heptanol): 1.9%    10.2 2-Propylheptanol+1.0 PO+3 EO

The procedure was as in example 10.1. However, 2.0 mol of propyleneoxide and 6.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 1.3%    10.3 2-Propylheptanol+1.2 PO+3 EO

The procedure was as in example 10.1. However, 2.4 mol of propyleneoxide and 6.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.9%    10.4 2-Propylheptanol+0.8 PO+4 EO

The procedure was as in example 10.1. However, 1.6 mol of propyleneoxide and 8.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 1.0%    10.5 2-Propylheptanol+1.0 PO+4 EO

The procedure was as in example 10.1. However, 2.0 mol of propyleneoxide and 8.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.7%    10.6 2-Propylheptanol+1.3 PO+4 EO

The procedure was as in example 10.1. However, 2.6 mol of propyleneoxide and 8.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.5%    10.7 2-Propylheptanol+0.6 PO+5 EO

The procedure was as in example 10.1. However, 1.2 mol of propyleneoxide and 10.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.8%    10.8 2-Propylheptanol+1.2 PO+5 EO

The procedure was as in example 10.1. However, 2.4 mol of propyleneoxide and 10.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.14%    10.9 2-Propylheptanol+1.0 PO+6 EO

The procedure was as in example 10.1. However, 2.0 mol of propyleneoxide and 12.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.12%    10.10 2-Propylheptanol+1.2 PO+6 EO

The procedure was as in example 10.1. However, 2.4 mol of propyleneoxide and 12.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.09%    10.11 2-Propylheptanol+1.3 PO+6 EO

The procedure was as in example 10.1. However, 2.6 mol of propyleneoxide and 12.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.06%    10.12 2-Propylheptanol+1.2 PO+7 EO

The procedure was as in example 10.1. However, 2.4 mol of propyleneoxide and 14.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.03%    10.13 2-Propylheptanol+1.3 PO+8 EO

The procedure was as in example 10.1. However, 2.6 mol of propyleneoxide and 16.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.02%    10.14 2-Propylheptanol+1.0 PO+10 EO

The procedure was as in example 10.1. However, 2.0 mol of propyleneoxide and 20.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.01%    10.15 2-Propylheptanol+1.0 PO+14 EO

The procedure was as in example 10.1. However, 2.0 mol of propyleneoxide and 28.0 mol of ethylene oxide were added.

-   Residual alcohol content (2-propyl-1-heptanol): 0.01%

A comparison of the values for the residual alcohol content of a productcontaining PO and EO determined arithmetically in each case from example8 and 9 with the values obtained experimentally for example 10 clearlyshows that the initial propoxylation and subsequent ethoxylation leadsto a significantly reduced residual alcohol content compared to thetheoretically expected value.

1. A mixture comprising alkoxylates of the formula (I)C₅H₁₁CH(C₃H₇)CH₂O(A)_(n)(B)_(m)H (I) wherein the mixture comprises 85%to 96% by weight of alkoxylats A1 wherein C₅H₁₁ is n-C₅H₁₁, and 4% to15% by weight of alkoxylates A2 wherein C₅H₁₁ is C₂H₅CH(CH₃)CH₂ and/orCH₃CH(CH₃)CH₂CH₂, wherein A is ethyleneoxy, B is C₃₋₁₀-alkyleneoxy ormixtures thereof, where groups A and B may be present in randomdistribution, alternately or in the form of two or more blocks in anyorder, n is a number from 0 to 30, m is a number from 1 to 8, andwherein the C₃₋₁₀-akyleneoxy or mixtures thereof is firstly added to theC₅H₁₁CH(C₃H₇)CH₂O-radical.
 2. The mixture as claimed in claim 1, whereinC₃H₇ is n-C₃H₇.
 3. The mixture as claimed in claim 1, wherein B ispropyleneoxy, and n is a number from 1 to
 20. 4. A process for preparingthe mixture as claimed in claim 1, the process comprising: reacting analcohol mixture with C₂₋₅-alkylene oxides under alkoxylation conditions,optionally in the presence of a double-metal cyanide compound ascatalyst.
 5. A method of preparing a product, the method comprising:combining the mixture of claim 1 with at least one substance to createthe product, wherein the at least one substance is selected from thegroup consisting of a soap, an anionic surfactant, an organic acid, aninorganic acid, a solvent, a complexing agent, a polymer, a copolymer,an alkali donor, a perfume oil, an oxidizing agent, an enzyme, andcombinations thereof, and wherein the product is an emulsifier, a foamregulator or a wetting agent for hard surfaces.
 6. The method as claimedin claim 5, wherein the product is a detergent, a surfactant formulationfor the cleaning of hard surfaces, a humectant, a cosmetic formulation,a pharmaceutical formulation, a crop protection formulation, a paint, acoating composition, an adhesive, a leather degreasing composition, aformulation for the textile industry, fiber processing, metal working,food industry, water treatment, paper industry, fermentation or mineralprocessing or a product to be comprised in emulsion polymerizations. 7.A washing, cleaning, wetting, coating, adhesive, leather degreasing,humectant or textile-treatment composition or cosmetic, pharmaceuticalor crop protection formulation comprising the mixture as claimed inclaim
 1. 8. The mixture as claimed in claim 2, wherein B ispropyleneoxy, and n is a number from 1 to
 20. 9. A process for thepreparation of the mixture as claimed in claim 2, the processcomprising: reacting an alcohol mixture with C₂₋₅-alkylene oxides underalkoxylation conditions, optionally in the presence of a double-metalcyanide compound as catalyst.
 10. A process for the preparation of themixture as claimed in claim 3, the process comprising: reacting thealcohol mixture with C₂₋₅-alkylene oxides under alkoxylation conditions,optionally in the presence of a double-metal cyanide compound catalyst.11. A washing, cleaning, wetting, coating, adhesive, leather degreasing,humectant or textile-treatment composition or cosmetic, pharmaceuticalor crop protection formulation comprising the mixture as claimed inclaim
 2. 12. A washing, cleaning, wetting, coating, adhesive, leatherdegreasing, humectant or textile-treatment composition or cosmetic,pharmaceutical or crop protection formulation comprising the mixture asclaimed in claim 3.